Mixtures of matrix materials and organic semiconductors capable of emission, use of the same and electronic components containing said mixtures

ABSTRACT

The present invention describes new types of material mixtures composed of at least two substances, one serving as a matrix material and the other being an emission material capable of emission, the latter comprising at least one element of atomic number greater than 20, and the use thereof in organic electronic components such as electroluminescent elements and displays.

The present invention relates to the use of novel materials and materialmixtures in organic electronic components such as electroluminescentelements, and to the use thereof in displays based thereon.

In a series of different types of applications which can be classifiedwithin the electronics industry in the widest sense, the use of organicsemiconductors as active components (=functional materials) has becomereality in recent times or is expected in the near future. For instance,light-sensitive organic materials (e.g. phthalocyanines) and organiccharge transport materials (generally triarylamine-based holetransporters) have already found use for several years in copyingmachines. The use of specific semiconducting organic compounds which arecapable of emission of light in the visible spectral region is juststarting to be introduced onto the market, for example in organicelectroluminescent devices. Their individual components, the organiclight-emitting diodes (OLEDs), have a very wide spectrum of applicationas:

-   1. white or colored backlighting for monochrome or multicolor    display elements (for example in pocket calculators, for mobile    telephones and other portable applications),-   2. large-surface area displays (for example traffic signs,    billboards and other applications),-   3. illumination elements in all colors and forms,-   4. monochrome or full-color passive matrix displays for portable    applications (for example mobile telephones, PDAs, camcorders and    other applications),-   5. full-color, large-surface area, high-resolution active matrix    displays for a wide variety of applications (for example mobile    telephones, PDAs, laptops, televisions and other applications).

The development of some of these applications is already very, faradvanced; nevertheless, there is still great technical need forimprovement.

Devices containing relatively simple OLEDs have already been introducedonto the market, as demonstrated by the car radios from Pioneer or adigital camera from Kodak with an organic display. However, there arestill considerable problems which are in need of urgent improvement:

-   1. For instance, the operative lifetime in particular of OLEDs is    still low, so that it has only been possible to date to commercially    realize simple applications.-   2. Although the efficiencies of OLEDs are acceptable, even    improvements are still desired here too, specifically for portable    applications.-   3. The color coordinates of OLEDs, especially in the red, are not    good enough. Particularly the combination of good color coordinates    with high efficiency has to be improved.-   4. The aging processes are generally accompanied by a rise in the    voltage. This effect makes voltage-driven organic electroluminescent    devices, for example displays or display elements, difficult or    impossible. However, voltage-driven addressing is more complex and    costlier precisely in this case.-   5. The required operating voltage is quite high specifically in the    case of efficient phosphorescent OLEDs and therefore has to be    reduced in order to improve the power efficiency. This of great    significance specifically for portable applications.-   6. The required operating current has likewise been reduced in the    last few years, but has to be reduced still further in order to    improve the power efficiency. This is particularly important    specifically for portable applications.-   7. The multitude of layers makes the construction of OLEDs complex    and technologically very complicated. It would therefore be    desirable to be able to realize OLEDs with a simpler layer structure    which requires fewer layers, but still has good or even improved    properties.

The reasons mentioned above under 1 to 7 make improvements in theproduction of OLEDs necessary.

A development in this direction which has emerged in recent years is theuse of organometallic complexes which exhibit phosphorescence instead offluorescence [M. A. Baldo, S. Lamansky, P. E. Burrows, M. E. Thompson,S. R. Forrest, Appl. Phys. Lett. 1999, 75, 4-6]. For quantum-mechanicalreasons, up to four times the quantum efficiency, energy efficiency andpower efficiency are possible using organometallic compounds. Whetherthis new development will establish itself firstly depends strongly uponwhether corresponding device compositions can be found which can alsoutilize these advantages (triplet emission=phosphorescence compared tosinglet emission=fluorescence) in OLEDS. The essential conditions forpractical use here are in particular a high operative lifetime, a highstability against thermal stress and a low use and operating voltage inorder to enable mobile applications.

The general structure of organic electroluminescent devices isdescribed, for example, in U.S. Pat. No. 4,539,507 and U.S. Pat. No.5,151,629, and also EP 01202358.

Typically, an organic electroluminescent device consists of a pluralityof layers which are applied by means of vacuum methods or variousprinting methods. These layers are specifically:

-   1. a carrier plate=substrate (typically glass or plastics films).-   2. A transparent anode (typically indium tin oxide, ITO).-   3. A hole injection layer (Hole Injection Layer=HIL):

for example based on copper-phthalocyanine (CuPc) or conductive polymerssuch as polyaniline (PANI) or polythiophene derivatives (such as PEDOT).

-   4. One or more hole transport layers (Hole Transport Layer=HTL):    typically based on triarylamine derivatives, for example    4,4′,4″-tris(N-1-naphthyl-N-phenylamino)triphenylamine (NaphDATA) as    the first layer and N,N′-di(naphth-1-yl)-N,N′-diphenylbenzidine    (NPB) as the second hole transport layer.-   5. One or more emission layers (Emission Layer=EML): this layer (or    layers) may coincide partly with layers 4 to 8, but consists    typically of matrix materials, such as    4,4′-bis(carbazol-9-yl)biphenyl (CBP), doped with fluorescent dyes,    for example N,N′-diphenylquinacridone (QA), or phosphorescence dyes,    for example tris(2-phenylpyridyl)iridium (Ir(PPy)₃) or    tris(2-benzothiophenylpyridyl)iridium (Ir(BTP) 3). However, the    emission layer may also consist of polymers, mixtures of polymers,    mixtures of polymers and low molecular weight compounds or mixtures    of different low molecular weight compounds.-   6. A hole-blocking layer (Hole-Blocking Layer=HBL): this layer may    coincide partly with layers 7 and 8. It consists typically of BCP    (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline=bathocuproin) or    bis(2-methyl-8-quinolinolato)(4-phenylphenolato)aluminum(III)    (BAlq).-   7. An electron transport layer (Electron Transport Layer=ETL):    usually based on aluminum tris-8-hydroxyquinolate (AlQ₃)-   8. An electron injection layer (Electron Injection Layer=EIL): this    layer may coincide partly with layer 4, 5, 6 and 7, or a small    portion of the cathode is specially treated or specially deposited.-   9. A further electron injection layer (Electron Injection    Layer=EIL): a thin layer consisting of a material having a high    dielectric constant, for example LiF, Li₂O, BaF₂, MgO, NaF.-   10. A cathode: here, generally metals, metal combinations or metal    alloys having a low work function are used, for example Ca, Ba, Cs,    Mg, Al, In, Mg/Ag.

This whole device is appropriately (depending on the application)structured, contacted and finally also hermetically sealed, since thelifetime of such devices is generally shortened drastically in thepresence of water and/or air. The same also applies to what are known asinverted structures in which the light is emitted from the cathode. Inthese inverted OLEDs, the anode consists, for example, of Al/Ni/NiOx orAl/Pt/PtOx or other metal/metal oxide combinations which have a HOMOgreater than 5 eV. The cathode consists of the same materials asdescribed in point 9 and 10, with the difference that the metal, forexample Ca, Ba, Mg, Al, In, etc, is very thin and thus transparent. Thelayer thickness is below 50 nm, better below 30 nm, even better below 10nm. A further transparent material can also be applied to thistransparent cathode, for example ITO (indium tin oxide), IZO (indiumzinc oxide), etc.

In the abovementioned structure, the matrix material of the emissionlayer (EML) plays a particular role. The matrix material has to enableor improve the charge transport of holes and/or electrons, and/or enableor improve charge carrier recombination, and, if appropriate, transferthe energy arising in the recombination to the emitter. In theelectroluminescent devices based on phosphorescent emitters, this taskhas to date been assumed predominantly by matrix materials which containcarbazole units.

However, matrix materials which contain carbazole units, for example thefrequently used 4,4′-bis(N-carbazolyl)biphenyl (CBP), have somedisadvantages in practice. These can be seen, inter alia, in the oftenshort to very short lifetime of the devices produced with them and thefrequently high operating voltages which lead to low power efficiencies.In addition, it has been found that, for energetic reasons, CBP isunsuitable for blue-emitting electroluminescent devices, which resultsin a very poor efficiency. Moreover, the structure of the devices isvery complex when CBP is used as the matrix material, since a holeblocking layer and an electron transport layer have to be used inaddition. When these additional layers are not used, as described, forexample, by Adachi et al. (Organic Electronics 2001, 2, 37) goodefficiencies are observed but only at extremely low brightnesses, whilethe efficiency at higher brightness, as required for application, islower by more than one order of magnitude. Thus, high voltages arerequired for high brightnesses, so that the power efficiency is very lowhere, which is unsuitable especially for passive matrix applications.

It has now been found that, surprisingly, the use of certain matrixmaterials in combination with certain emitters leads to distinctimprovements over the prior art, especially in relation to theefficiency and in combination with a greatly increased lifetime. Inaddition, a distinctly simplified layer structure of the OLEDs ispossible with these matrix materials, since neither a separate holeblocking layer nor a separate electron transport and/or electroninjection layer has to be used. This is an enormous technologicaladvantage.

The use of the matrix materials described below in OLEDs which comprisephosphorescent emitters is just as novel as the underlying mixture. Theuse of analogous materials in simple devices, as emission materialsthemselves or as materials in the emission layer in combination withfluorescent emitters, has already been described in occasionalreferences in the literature (e.g.: JP 06192654). There is likewise adescription (WO 04/013080) of aroyl derivatives of spirobifluorene whichcan also be used in OLEDs, but without reference to triplet emission,electrophosphorescence or matrix materials therefor; this can thus beevaluated as a coincidental disclosure. The novelty of the inventiondescribed below is not prejudiced by the abovementioned descriptions,since the use of the matrix materials described below in OLEDs incombination with phosphorescent emitters is novel.

The invention therefore provides mixtures comprising

-   -   at least one matrix material A which contains a structural unit        of the form C=Q in which Q has at least one nonbonding electron        pair and represents the element O, S, Se or N, and which can in        some cases also form glasslike layers, and    -   at least one emission material B which is capable of emission        and is a compound which, upon suitable excitation, emits light,        and contains at least one element of atomic number greater than        20.

The inventive mixtures are preferably those which comprise at least onematrix material A for which the glass transition temperature T_(g) ofthe pure substance A is greater than 70° C., preferably greater than100° C., more preferably greater than 130° C.

The matrix material A present in the above-described mixtures ispreferably at least one compound of the formula (1), formula (2) and/orformula (3)

where the symbols and indices are each defined as follows:

-   X is the same or different at each instance and is O, S or Se;-   Y at each instance is N;-   R¹, R², R³ is the same or different at each instance and is H, CN, a    straight-chain, branched or cyclic alkyl, alkoxy or alkylamino group    having from 1 to 40 carbon atoms, in which one or more nonadjacent    CH₂ groups may be replaced by —R⁴C═CR⁴—, —C≡C—, C═O, C═S, C═Se,    C═NR⁴, —O—, —S—, —NR⁵— or —CONR⁶—, and in which one or more hydrogen    atoms may be replaced by F, Cl, Br, I, or an aromatic or    heteroaromatic system having from 1 to 40 carbon atoms, in which one    or more hydrogen atoms may be replaced by F, Cl, Br, I, and which    may be substituted by one or more nonaromatic R¹ radicals, and a    plurality of substituents R¹ and/or R¹, R², either on the same ring    or on the two different rings, may together in turn form a further    mono- or polycyclic, aliphatic or aromatic ring system; with the    proviso that R¹=R²=R³≠hydrogen;-   R⁴, R⁵, R⁶ are the same or different at each instance and are H or    an aliphatic or aromatic hydrocarbon radical having from 1 to 20    carbon atoms.

In the context of this invention, an aromatic or heteroaromatic systemshall be understood to mean a system which does not necessarily containonly aromatic or heteroaromatic groups, but in which a plurality ofaromatic or heteroaromatic groups may also be interrupted by a shortnonaromatic unit (<10% of the atoms, preferably <5% of the atoms), forexample sp³-hybridized C, O, N, etc. For example, aromatic systemsshould thus also be understood to mean systems such as9,9′-spirobifluorene, 9,9-diarylfluorene, triarylamine, diphenyl ether,etc.

Even if this is evident from the definition above, it is explicitlypointed out here once again that the R¹ or R² radical may also be asubstituted or unsubstituted vinyl group or a corresponding derivative,i.e. that the compound of the formula (1) may also be an α,β-unsaturatedcarbonyl compound, or the compound of the formula (2) or (3) may also bean α,β-unsaturated imine.

Particularly suitable compounds of the formula (1) to (3) have beenfound to be compounds which do not have a planar structure. On thestructural unit of the form C=Q, appropriate substituents can ensuredeviation of the overall structure from planarity. This is the caseespecially when at least one of the substituents R¹, R² and/or R³contains at least one sp³-hybridized carbon, silicon, germanium and/ornitrogen atom, which thus has approximately tetrahedral, or, in the caseof nitrogen, pyramidal bonding geometry. In order to achieve a distinctdeviation from planarity, it is preferred when at least one of thesp³-hybridized atoms is a secondary, tertiary or quaternary atom, morepreferably a tertiary or quaternary atom, in the case of carbon, siliconor germanium most preferably a quaternary atom. A secondary, tertiary orquaternary atom is understood respectively to mean an atom having two,three or four substituents other than hydrogen.

Preference is further given to compounds which, in at least one of theR¹ to R³ radicals, contain a 9,9′-spirobifluorene derivative, preferablybonded via the 2- and/or 2,7- and/or 2,2′- and/or 2,2′,7- and/or2,2′,7,7′-position, a 9,9-disubstituted fluorene derivative, preferablybonded via the 2- and/or 2,7-position, a 6,6- and/or 12,12-di- ortetrasubstituted indenofluorene derivative, a triptycene derivative,preferably bonded via the 9- and/or 10-position, a dihydrophenanthrenederivative, preferably bonded via the 2- and/or 2,7- and/or 3- and/or3,6-position, or a hexaarylbenzene derivative, preferably bonded via thep-position, to the aromatic(s).

Particular preference is given to compounds which contain a9,9′-spirobifluorene derivative in at least one of the R¹ to R³radicals.

Preference is once again further given to compounds which contain asubstituted or unsubstituted 2-biphenyl or a substituted orunsubstituted 2-biphenyl ether in at least one of the R¹ to R³ radicals.

Preference is further given to compounds which have a dendriticstructure. Preference is also given to 1,3,5-trisubstituted benzeneketones and corresponding oligo ketones which are obtainable, forexample, according to N. Nakamura et al., J. Amer. Chem. Soc. 1992, 114,1484, or according to K. Matsuda et al., J. Amer. Chem. Soc. 1995, 177,5550.

In order to avoid misunderstanding, it is emphasized at this point thatmatrix materials A with the structural unit C=Q of course do not meanaromatic systems which contain partial C═N double bonds in the ring, forexample pyrimidines, pyrazines, etc.

Preference is likewise given to mixtures which comprise, as a matrixmaterial A, at least one compound of the formula (4) to (9)

where the symbols X, Y, R¹, R², R³ R⁴, R⁵ and R⁶ are each as definedunder formulae (1) to (3) and

-   Z is the same or different at each instance and is CR¹ or N.

Particular preference is given to organic mixtures which contain atleast one of the matrix materials A described above by formula (1) to(9) in which:

-   X at each instance is O or S;-   Y at each instance is N;-   Z at each instance is CR¹;-   R¹, R², R³ is the same or different at each instance and is H, a    straight-chain, branched or cyclic alkyl group which has from 1 to    40 carbon atoms and preferably no hydrogen atoms in the α-position    to the keto or imine function, in which one or more nonadjacent CH₂    groups may be replaced by —R⁴C═CR⁴—, —C≡C—, C═O, C═S, C═Se, C═NR⁴,    —O—, —S—, —NR⁵— or —CONR⁶—, and in which one or more hydrogen atoms    may be replaced by F, Cl, Br, I, or    -   an aromatic or heteroaromatic system having from 1 to 40 carbon        atoms, in which one or more hydrogen atoms may be replaced by F,        Cl, Br, I, and which may be substituted by one or more        nonaromatic R¹ radicals, and a plurality of substituents R¹        and/or R¹, R², either on the same ring or on the different        rings, may together in turn form a further mono- or polycyclic,        aliphatic or aromatic ring system,-   R⁴, R⁵, R⁶ are each as described under formula (1) to (3).

Preference is likewise given to mixtures which contain, as a matrixmaterial A, at least one compound of the formula (10) to (15)

Where the symbols Z, Y and R¹ to R⁶ are each defined as described underformula (1) to (9), and the further symbols and indices are:

-   Ar is the same or different at each instance and is an aromatic or    heteroaromatic system having from 2 to 40 carbon atoms, preferably    having from 4 to 30 carbon atoms, in which one or more hydrogen    atoms may be replaced by F, Cl, Br, I, and which may be substituted    by one or more nonaromatic R¹ radicals, and a plurality of    substituents R¹, either on the same ring or on different rings, may    together in turn form a further mono- or polycyclic, aliphatic or    aromatic ring system;-   n is the same or different at each instance and is 0 or 1.

The reason for the preference for these materials of the formula (10) to(15) is in particular their high glass transition temperatures.Depending on the substitution pattern, these are typically above 70° C.and usually above 100° C.

The present invention likewise provides the novel compounds of theformula (10a) to (15)

in which the symbols Z, Y, Ar and R¹ to R⁶ are each as defined above,and the further symbols used are:

-   E is the same or different at each instance and is C or N;-   R⁷ is the same or different at each instance and is an alkyl, alkoxy    or alkylamino group having from 1 to 40 carbon atoms, in which one    or more CH₂ groups may also be replaced by —R⁴C═CR⁴—, —C≡C—, C═O,    C═S, C=Se, C═NR⁴, —O—, —S—, —NR⁴ or —CONR⁴—, and in which one or    more hydrogen atoms may also be replaced by F, Cl, Br, I, with the    proviso that no hydrogen atoms are bonded in the α-position to the    carbonyl group, or an aromatic group which may optionally be    substituted by halogen, alkyl, trifluoromethyl, hydroxyl, —SH,    —S-alkyl, alkoxy, intro, cyano, —COOH, —COoalkyl, —NH₂, -Nalkyl,    benzyl or benzoyl,    -   or a larger aromatic system having from 2 to 40 carbon atoms,        preferably from 4 to 30 carbon atoms, for example        9,9′-spirobifluorene, fluorene, triarylamine, etc., in which one        or more hydrogen atoms may be replaced by F, Cl, Br, I, and        which may be substituted by one or more nonaromatic R¹ radicals,        and a plurality of substituents R¹ may in turn form a further        mono- or polycyclic, aliphatic or aromatic ring system;-   A¹ at each instance is R⁸ or CO—R⁷ when X═C or is a free electron    pair when X═N;-   A² at each instance is R⁸ or CO—R⁷ when X═C or is a free electron    pair when X═N;-   A³ at each instance is R⁸ or CO—R⁷ when X═C or is a free electron    pair when X═N;-   R⁸ is the same or different at each instance and is H, F, Cl, Br, I,    CN, NO₂, a straight-chain or branched or cyclic alkyl group having    from 1 to 40 carbon atoms, in which one or more nonadjacent CH₂    groups may be replaced by —R⁴C═CR⁴—, —C≡C—, C═S, C═Se, C═NR⁴, —O—,    —S—, —NR⁴— or —CONR⁴—, and in which one or more hydrogen atoms may    be replaced by F, Cl, Br, I, or    -   an aromatic or heteroaromatic system having from 1 to 40 carbon        atoms, in which one or more hydrogen atoms may be replaced by F,        Cl, Br, I, and which may be substituted by one or more        nonaromatic R¹ radicals, and a plurality of substituents R¹        and/or R¹/R⁴, either on the same ring or on the different rings,        may together in turn form a further mono- or polycyclic,        aliphatic or aromatic ring system;        with the proviso that, for the compound of the formula (10a),        only the following combinations are permitted for the symbols        described, where R⁸ and R⁴ can be selected freely according to        the definition:    -   when R⁷ is an alkyl group without α-hydrogen atoms, the symbols        Z, E, A¹, A² and A³ can be selected freely according to the        definition;    -   when R⁷ is an aromatic group and at least one Z is N, the        symbols E, A¹, A² and A³ can be selected freely according to the        definition;    -   when R⁷ is an aromatic group and at least one Z is a CR¹ group        where R¹ is other than H, the symbols E, A¹, A² and A³ can be        selected freely according to the definition;

when R⁷ is an aromatic group and all Z are CH and at least one symbol Eis N, the symbols A¹, A² and A³ can be selected freely according to thedefinition;

when R⁷ is an aromatic group, all Z are CH and all E are C, at least oneof the symbols A¹, A² and/or A³ has to be an R⁸ group other than alkyl,while the two other groups can be selected freely according to thedefinition;

when R⁷ is an aromatic group, all Z are CH, all E are C and the twosymbols A¹ and A² are selected freely according to the definition, atleast one of the two symbols being a group other than H, the symbol A³is a CO—R⁷ group where R⁷ here can be selected freely according to thedefinition;

when R⁷ is a larger aromatic system, for example fluorene,spirobifluorene, triarylamine, etc., the symbols Z, E, A¹, A² and A³ canbe selected freely according to the definition.

For the sake of clarity, the permitted combinations of the symbols R⁷,Z, E, A¹, A² and A³ for compounds of the formula (10a) are compiled intable 1. TABLE 1 Possible combinations of the symbols R⁷, Z, E, A¹, A²and A³ for compounds of the formula (10a). R⁷ Z E A¹ A² A³ alkyl withoutany according to any according to any according to any according to anyaccording to α-H the definition the definition the definition thedefinition the definition aromatic group at least 1 Z = N any accordingto any according to any according to any according to the definition thedefinition the definition the definition aromatic group at least 1 Z =CR¹ any according to any according to any according to any according towhere at the definition the definition the definition the definitionleast 1 R¹ is not H aromatic group all Z = CH at least 1 E = N anyaccording to any according to any according to the definition thedefinition the definition aromatic group all Z = CH All E = C R⁸ is notalkyl any according to any according to the definition the definitionaromatic group all Z = CH all E = C any according to R⁸ is not alkyl anyaccording to the definition the definition aromatic group all Z = CH allE = C any according to any according to R⁸ is not alkyl the definitionthe definition aromatic group all Z = CH all E = C any according to anyaccording to CO-R⁷ (R⁷ the definition, the definition according to theis not H definition) aromatic group all Z = CH all E = C any accordingto any according to CO-R⁷ (R⁷ the definition the definition, accordingto the is not H definition) larger aromatic any according to anyaccording to any according to any according to any according to system(e.g. the definition the definition the definition the definition thedefinition fluorene, spirobifluorene, . . . )

Preference is given to compounds in which at least one R7 groupdescribes a larger aromatic system, for example fluorene,spirobifluorene, arylamine, etc.

Preference is further given to compounds in which at least one R⁷ groupis an alkyl group as defined above without α-hydrogen atoms.

Preference is further given to compounds in which at least one of thesymbols A, B and/or D is an aromatic or heteroaromatic system.

Preference is further given to the compounds which contain more than onespirobifluorene unit.

Preference is further given to compounds in which at least one of thesymbols Z or E is N.

Preference is further given to compounds which contain more than oneketo function, i.e. diketones or oligoketones.

The present invention is illustrated in detail by the examples of matrixmaterials A which follow, without any intention to restrict it thereto.Those skilled in the art can prepare further matrix materials and usethem in inventive mixtures from the description and the adduced exampleswithout any inventive activity.

Example 1 Example 2

Example 3 Example 4

Example 5 Example 6

Example 7 Example 8

Example 9 Example 10

Example 11 Example 12

Example 13

Example 14

Example 15 Example 16

Example 17 Example 18

Example 19 Example 20

Example 21

Example 22

Example 23 Example 24

Example 25 Example 26

Example 27 Example 28

Example 29 Example 30

Example 31 Example 32

Example 33 Example 34

Example 35

Example 36

Example 37 Example 38

Example 39 Example 40

Example 41 Example 42

Example 43

Example 44

Example 45 Example 46

Example 47 Example 48

Example 49 Example 50

Example 51

The above-described matrix materials A, for example according toexamples 26, 27 and 28, may also find use, for example, as comonomersfor obtaining corresponding conjugated, semiconjugated or elsenonconjugated polymers, or as the core of dendrimers, for exampleaccording to examples 29, 30 and 31. The corresponding polymerization ispreferably effected via the halogen functionality. For instance, theycan be polymerized, inter alia, into soluble polyfluorenes (for exampleaccording to EP 842208 or WO 00/22026), poly-spirobifluorenes (forexample according to EP 707020 or EP 894107), poly-para-phenylenes (forexample according to WO 92/18552), polycarbazoles or else polythiophenes(for example according to EP 1028136).

The above-described conjugated, semiconjugated or nonconjugated polymersor dendrimers which contain one or more structural units of the formula(1) or (15) may be used as the matrix material in organicelectroluminescent devices.

In addition, the inventive matrix materials A may also be functionalizedfurther by, for example, the abovementioned reaction types, and thusconverted to extended matrix materials A. Here, examples include thefunctionalization with arylboronic acids according to SUZUKI or withamines according to HARTWIG-BUCHWALD.

In order to find use as a functional materiel, the inventive matrixmaterials A or their mixtures or the polymers or dendrimers containingmatrix materials A, if appropriate together with the emitters B, areapplied to a substrate in the form of a film by commonly known methodsfamiliar to those skilled in the art, such as vacuum evaporation,evaporation in a carrier gas stream or else from solution byspincoating, or by various printing processes (for example inkjetprinting, offset printing, LITI printing, etc.).

The use of printing processes can have advantages with regard to thescalability of manufacture, and with regard to the adjustment of mixingratios in blend layers used.

The above-described matrix materials are used in combination withphosphorescence emitters. These mixtures feature the presence, as anemitter B, of at least one compound, which is characterized in that itemits light upon suitable excitation and also contains at least one atomof atomic number greater than 20, preferably greater than 38 and lessthan 84, more preferably greater than 56 and less than 80.

The phosphorescence emitters used in the above-described mixtures arepreferably compounds which contain molybdenum, tungsten, rhenium,ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, goldor europium.

Particularly preferred mixtures comprise, as emitter B, at least onecompound of the formula (16) to (19)

where the symbols used are:

-   DCy is the same or different at each instance and is a cyclic group    which contains at least one donor atom, preferably nitrogen or    phosphorus, via which the cyclic group is bonded to the metal atom,    and which may in turn bear one or more substituents R⁹; the DCy and    CCy groups are joined together via a covalent bond;-   CCy is the same or different at each instance and is a cyclic group    which contains a carbon atom via which the cyclic group is bonded to    the metal and which may in turn bear one or more substituents R⁹;-   R⁹ is the same or different at each instance and is H, F, Cl, Br, I,    NO₂, CN, a straight-chain or branched or cyclic alkyl or alkoxy    group having from 1 to 40 carbon atoms, in which one or more    nonadjacent CH₂ groups may be replaced by —CR⁴═CR⁴—, —C≡C—, C═O,    C═S, C═Se, C═NR⁴, —O—, —S—, —NR⁵— or —CONR⁶—, and in which one or    more hydrogen atoms may be replaced by F, or an aromatic or    heteroaromatic system which has from 4 to 40 carbon atoms and may be    substituted by one or more nonaromatic R⁹ radicals; and a plurality    of substituents R⁹, either on the same ring or on the two different    rings, may together in turn form a further mono- or polycyclic,    aliphatic or aromatic ring system;-   L is the same or different at each instance and is a bidentate    chelating ligand, preferably a diketonate ligand;-   R⁴, R⁵, R⁶ is the same or different at each instance and is H or an    aliphatic or aromatic hydrocarbon radical having from 1 to 20 carbon    atoms.

Examples of the above-described emitters can be taken, for example, fromthe applications WO 00/70655, WO 01/41512, WO 02/02714, WO 02/15645, EP1191613, EP 1191612, EP 1191614, WO 03/099959, WO 03/084972, WO03/040160, WO 02/081488, WO 02/068435 and DE 10238903.9; these arehereby considered as part of the application by reference.

The inventive mixture contains between 1 to 99% by weight, preferablybetween 3 and 95% by weight, more preferably between 5 and 50% byweight, in particular between 7 and 20% by weight, of emitter B based onthe overall mixture of emitter B and matrix material A.

The present invention further provides electronic components, inparticular organic electroluminescent devices (OLEDs), organic solarcells (O-SCs), organic field-effect transistors (O-FETs) or else organiclaser diodes (O-laser), comprising the inventive mixture of matrixmaterial A and emission material B. Particular preference is given toorganic electroluminescent devices which have an emitting layer (EML)comprising an inventive mixture of at least one matrix material A and atleast one emission material B capable of emission.

Preference is given in particular to organic electroluminescent deviceswhich contain, in the emitting layer (EML), at least one inventivemixture, the glass transition temperature T_(g) of the pure substance ofthe matrix material A being greater than 70° C.

Apart from the cathode, the anode and the emitting layer, the organicelectroluminescent device may comprise further layers, for example holeinjection layer, hole transport layer, hole blocking layer, electrontransport layer and/or electron injection layer. However, it should bepointed out here that not necessarily each of these layers need bepresent.

For example, it has been found that an OLED which contains neither aseparate hole blocking layer nor a separate electron transport layershows very good results in the electroluminescence, in particular avoltage which is once again distinctly lower and higher powerefficiency. This is particularly surprising since a corresponding OLEDwith a carbazole-containing matrix material without hole blocking andelectron transport layer exhibits only very low power efficiencies,especially at high brightness (cf. Adachi et al., Organic Electronics2001, 2, 37). The invention thus further provides an organicelectroluminescent device comprising an inventive mixture which, withoutuse of a hole blocking layer, directly adjoins the electron transportlayer, or which, without use of a hole blocking layer and of an electrontransport layer, directly adjoins the electron injection layer or thecathode.

It has likewise been found that an OLED which does not contain anyseparate hole injection layer, but rather only one or more holetransport layers (triarylamine layers) directly on the anode likewiseexhibits very good results in the electroluminescence. This structurethus also forms part of the subject matter of the present invention.

The inventive organic electroluminescent devices exhibit higherefficiency, distinctly longer lifetime and, especially without use of ahole blocking and electron transport layer, distinctly lower operatingvoltages and higher power efficiencies than prior art OLEDs whichcomprise CBP as the matrix material. Omission of the hole blocking andelectron transport layers additionally distinctly simplifies thestructure of the OLED, which constitutes a considerable technologicaladvantage.

The preferred embodiments of the inventive mixtures of matrix material Aand emission material B also apply to the inventive electroniccomponents, in particular to the organic electroluminescent devices(OLEDs), organic solar cells (O-SCs), organic field-effect transistors(O-FETs) or else organic laser diodes (O-laser). To avoid unnecessaryrepetitions, another enumeration at this point is dispensed with.

In the present application text and also in the examples which follow,the aim is solely organic light-emitting diodes and the correspondingdisplays. In spite of this restriction of the description, it ispossible for those skilled in the art without any further inventiveactivity to produce and employ corresponding inventive layers from theinventive mixtures, especially in OLED-like or related applications.

EXAMPLES

1. Synthesis of Matrix Materials A:

The syntheses which follow were, unless stated otherwise, carried outunder a protective gas atmosphere in dried solvents. The reactants werepurchased from ALDRICH [copper(I) cyanide, acetyl chloride,N-methylpyrrolidinone (NMP)]. 2-Bromo-9,9′-spirobifluorene,2,7-dibromo-9,9′-spirobifluorene (J. Pei et al., J. Org. Chem. 2002,67(14), 4924-4936) and 9,9′-spirobifluorene-2,2′-dicarbonyl chloride (V.A. Montero et al., Tetrahedron Lett. 1991, 32(39), 5309-5312) wereprepared by literature methods.

Example 1 Bis(9,9′-spirobifluoren-2-yl) ketone

A: 2-cyano-9,9′-spirobifluorene

A suspension of 158.1 g (0.4 mol) of 2-bromo-9,9′-spirobifluorene and89.6 g (1 mol) of copper(I) cyanide in 1100 ml of NMP was heated to 160°C. for 16 h. After cooling to 30° C., the mixture was admixed with 1000ml of saturated ammonia solution and stirred for a further 30 min. Theprecipitate was filtered off with suction, washed three times with 300ml of saturated ammonia solution and three times with 300 ml of water,and suction-dried. After the solid had been dissolved in 1000 ml ofdichloromethane, the solution was dried over sodium sulfate, filteredthrough silica gel and concentrated to dryness. The thus obtained crudeproduct was recrystallized once from dioxane:ethanol (400 ml:750 ml).After the crystals had been dried under reduced pressure at 80° C., 81.0g (237 mmol), corresponding to 59.3% of theory, were obtained.

¹H NMR (CDCl₃: δ [ppm]=7.92-7.85 (m, 4H), 7.66-7.65 (m, 1H), 7.44-7.39(m, 3H), 7.22-7.19 (m, 1H), 7.15-7.11 (m, 2H), 6.99-6.98 (M, 1H),6.79-6.78 (m, 1H), 6.69-6.67 (m, 2H).

B: Bis(9,9′-spirobifluoren-2-yl) ketone

From a solution of 98.8 g (250 mmol) of 2-bromo-9,9′-spirobifluorene and6 ml of 1,2-dichloroethane in 1000 ml of THF and 7.1 g (290 mmol) ofmagnesium, the corresponding Grignard reagent was prepared at boiling. Asolution of 85.4 g (250 mmol) of 2-cyano-9,9′-spirobifluorene in amixture of 300 ml THF and 1000 ml of toluene was added dropwise at 0-5°C. to this Grignard solution over 15 min. Subsequently, the mixture washeated under reflux for 6 h. After cooling, a mixture of 35 ml of 10NHCl, 400 ml of water and 600 ml of ethanol was slowly added dropwise.After stirring at room temperature for 16 h, the solid was filtered offwith suction and washed three times with 200 ml of ethanol. The solidwas recrystallized four times from NMP (5 ml/g) and subsequentlysublimed under high vacuum (T=385° C., p=5×10⁻⁵ mbar). The yield at apurity of >99.9% by HPLC was 52.1 g (79 mmol), corresponding to 31.6% oftheory.

T_(g)=165° C., T_(m)=385° C.

¹H NMR (CDCl₃): δ [ppm]=7.87-7.85 (m, 2H), 7.83-7.81 (m, 4H), 7.78-7.86(m, 2H), 7.60-7.58 (m, 2H), 7.39-7.34 (m, 6H), 7.18-7.17 (m, 2H),7.16-7.13 (m, 2H), 7.10-7.07 (m, 4H), 6.34-6.32 (m, 2H), 6.70-6.69 (m,4H).

Example 2 2,2′-bis(benzoyl)spiro-9,9′-bifluorene

A suspension of 160.0 g (1.2 mol) of anhydrous aluminum chloride in 600ml of 1,2-dichloroethane was admixed dropwise with good stirring with132 ml (1.1 mol) of benzoyl chloride. A solution of 158.2 g (0.5 mol) ofspiro-9,9′-bifluorene in 600 ml of 1,2-dichloroethane was added dropwiseto this mixture at such a rate that the temperature did not exceed 25°C. After full addition, the mixture was stirred at room temperature foranother 1 h. Subsequently, the reaction mixture was poured onto anefficiently stirred mixture of 1000 g of ice and 260 ml of 2Nhydrochloric acid. The organic phase was removed and washed twice with500 ml of water. After the organic phase had been concentrated to avolume of approx. 200 ml and 500 ml of ethanol had been added, the finecrystalline precipitate which had formed was filtered off with suctionand washed with ethanol. The solid was recrystallized repeatedly fromtoluene and subsequently sublimed under high vacuum (T=290° C., p=5×10⁻⁵mbar). The yield at a purity of >99.9% by HPLC was 191.5 g (365 mmol),corresponding to 73.0% of theory.

T_(g)=99° C., T_(m)=281° C.

¹H NMR (CDCl₃): δ [ppm]=7.90 (m, 4H), 7.78 (m, 2H), 7.67 (m, 4H), 7.51(m, 2H) 7.43-7.37 (m, 6H), 7.31 (m, 2H), 7.20 (m, 2H), 6.78 (m, 2H)

Example 3 2,2′-bis(2-fluorobenzoyl)spiro-9,9′-bifluorene

Procedure analogous to example 2. Use of 174.4 g (1.1 mol) of2-fluorobenzoyl chloride. The solid was recrystallized repeatedly frombutanone and toluene and subsequently sublimed under high vacuum (T=250°C., p=5×10⁻⁵ mbar). The yield at a purity of >99.9% by HPLC was 192.8 g(344 mmol), corresponding to 68.8% of theory.

T_(g)=96° C., T_(m)=228° C.

¹H NMR (CDCl₃): δ [ppm]=7.90 (m, 4H), 7.77 (m, 2H), 7.48-7.40 (m, 6H),7.37 (m, 2H), 7.21-7.18 (m, 4H), 7.09 (m, 2H) 6.77 (M, 2H).

¹⁹F {¹H} NMR (CDCl₃): δ [ppm]=−111.7 (s)

Example 4 2.7-bis(2-spiro-9,9′-bifluorenylcarbonyl)spiro-9,9′-bifluorene

Procedure analogous to example 1B. Use of 59.3 g (125 mmol) of2,7-dibromospiro-9,9′-bifluorene. Sublimation at T=410° C. Yield 77.1 g(77 mmol), corresponding to 61.6% of theory.

T_(g)=209° C., T_(m)=401° C.

¹H NMR (CDCl₃): δ [ppm]=7.87-7.75 (m, 12H), 7.61-7.56 (m, 4H), 7.40-7.34(m, 8H), 7.18-7.14 (m, 6H), 7.11-7.07 (m, 6H), 6.74-6.67 (m, 8H).

Example 52,2′-bis(2-spiro-9,9′-bifluorenyl-carbonyl)spiro-9,9′-bifluorene

A: 9,9′-spirobifluorene-2,2′-dicarboxamide

220 ml of an ammonia solution (2N in ethanol) were admixed dropwise withgood stirring with 44.1 g (100 mmol) of9,9′-spirobifluorene-2,2′-dicarbonyl chloride dissolved in 200 ml ofdioxane. After the exothermic reaction had abated, the mixture wasstirred for a further 2 h, and the precipitated solid was filtered off,washed once with a mixture of 100 ml of water and 100 ml of EtOH, andonce with 200 ml of ethanol, and dried under reduced pressure. The yieldat a purity of >99.0% by ¹H NMR was 37.4 g (93 mmol), corresponding to93.0% of theory.

¹H NMR (DMSO-d6): δ [ppm]=8.13-8.10 (m, 4H), 8.01-7.99 (m, 2H), 7.89(br. s, 2H, NH₂), 7.47-7.44 (m, 2H), 7.23 (br. s, 2H, NH₂), 7.22-7.18(m, 2H), 7.14 (s, 2H), 6.66-6.64 (m, 2H)

B: 2,2′-dicyanospiro-9,9′-bifluorene

A suspension, cooled to −10° C., of 36.2 g (90 mmol) of9,9′-spirobifluorene-2,2′-dicarboxamide in 800 ml of DMF was admixeddropwise with 52.5 ml (720 mmol) of thionyl chloride at such a rate thatthe temperature did not rise above −5° C. The reaction mixture wasstirred at −10° C. for a further 3 h and then poured into a mixture of 2kg of ice and 500 ml of water. The hydrolyzate was extracted twice with500 ml each time of dichloromethane. The combined organic phases werewashed with 500 ml of water and with 500 ml of sat. sodium chloridesolution and dried over magnesium sulfate. The oil obtained afterconcentration of the organic phase crystallized after addition of 300 mlof ethanol in the form of white needles. The yield at a purity of >99.0%by ¹H NMR was 29.4 g (80 mmol), corresponding to 89.3% of theory.

¹H NMR (CDCl₂CDCl₂): δ [ppm]=7.95 (d, 2H), 7.92 (d, 2H) 7.71 (dd, 2H),7.47 (ddd, 2H), 7.24 (ddd, 2H), 6.96 (d, 2H), 6.75 (d, 2H).

C: 2,2′-bis(2-spiro-9,9′-bifluorenylcarbonyl)spiro-9,9′-bifluorene

Procedure analogous to example 1B. Use of 59.3 g (150 mmol) of2-bromo-9,9′-spirobifluorene and 27.5 g (75 mmol) of2,2′-dicyanospiro-9,9′-bifluorene. Sublimation at T=440° C. Yield 41.2 g(41 mmol), corresponding to 54.8% of theory.

T_(g)=213° C., T_(m)=430° C.

¹H NMR (CDCl₃): δ [ppm]=7.89-7.86 (m, 4H) 7.82-7.78 (m, 8H), 7.60 (br.m, 4H), 7.41-7.34 (m, 8H), 7.18-7.14 (m, 8H) 7.12-7.08 (4H), 6.75-6.70(m, 8H).

Example 6 Bis(9,9′-spirobifluoren-2-yl)-N-tert-butylimine

200 ml (200 mmol) of a 2M solution of titanium tetrachloride in toluenewere added dropwise over 30 min to a suspension, cooled to 0° C., of65.8 g (100 mmol) of bis(9,9′-spirobifluoren-2-yl) ketone (see example 1for preparation) in a mixture of 105.0 ml (1 mol) of tert-butylamine and1500 ml of toluene. Subsequently, the cooling bath was removed, and thereaction mixture, after attainment of room temperature, was stirred fora further 3 h and then heated under reflux for 60 h. After cooling, 1500ml of diethyl ether were added and the mixture was stirred at roomtemperature for a further 12 h. The suspension was filtered throughsilica gel, and the filtrate was concentrated to dryness, taken up in2000 ml of chloroform and filtered again through silica gel. The solidwhich remained after removal of the chloroform was recrystallized fourtimes from dioxane/ethanol (1:2 vv, 10 ml/g) and subsequently sublimedunder high vacuum (T=375° C., p=5×10⁻⁵ mbar). The yield at a purityof >99.9% by HPLC was 47.8 g (67 mmol), corresponding to 67.0% oftheory.

T_(g)=187° C., T_(m)=369° C.

¹H NMR (CDCl₃): δ [ppm]=7.89-7.72 (m, 7H), 7.62 (d, 1H) 7.37-7.26 (m,7H), 7.11-7.01 (m, 7H), 6.98 (s, 1H), 6.71 (d, 1H), 6.64-6.59 (m, 5H),6.44 (s, 1H), 0.83 (s, 9H).

Example 7 Bis(9,9′-spirobifluoren-2-yl)-N-phenylimine

Procedure analogous to example 6. Use of 45.6 ml (500 mmol) of aniline.Sublimation at T 370° C. Yield 53.7 g (73 mmol), corresponding to 73.2%of theory.

T_(g)=159° C., T_(m)=339° C.

¹H NMR (CDCl₃): δ [ppm]=7.82-7.74 (m, 6H), 7.70 (d, 1H), 7.65 (d, 1H),7.44 (s, 1H), 7.38-7.29 (m, 7H), 7.12-7.02 (m, 7H), 6.83 (t, 2H),6.72-6.64 (m, 5H), 6.52 (d, 2H), 6.38 (s, 1H), 6.30 (d, 2H).

2. Production of Organic Electroluminescent Devices which CompriseInventive Mixtures

OLEDs were produced by the general process outlined below. This ofcourse had to be adjusted in the individual case to the particularcircumstances (for example layer thickness variation to achieve optimalefficiency and color).

Inventive electroluminescent devices may be produced, for example, asfollows:

-   1. ITO-coated substrate: the substrate used is preferably ITO-coated    glass with a minimum level of or no ionic impurities, for example    flat glass from Merck-Balzers or Akaii. However, it is also possible    to use other ITO-coated transparent substrates, for example flexible    plastics films or laminates. The ITO has to combine a maximum    conductivity with a high transparency. ITO layer thicknesses between    50 and 200 nm have been found to be particularly suitable. The ITO    coating has to have maximum flatness, preferably with a roughness    below 2 nm. The substrates are initially precleaned with 4% Dekonex    solution in deionized water. Afterward, the ITO-coated substrate is    either treated with ozone for at least 10 minutes or with oxygen    plasma for a few minutes, or irradiated with an excimer lamp for a    short time.-   2. Hole injection layer (Hole Injection Layer ═HIL): the HIL used is    either a polymer or a low molecular weight substance. Particularly    suitable polymers are polyaniline (PANI) or polythiophene (PEDOT)    and derivatives thereof. They are usually 1 to 5% aqueous    dispersions which are applied in thin layers of layer thickness    between 20 and 200 nm, preferably between 40 and 150 nm, to the ITO    substrate by spincoating, inkjet printing or other coating    processes. Afterward, the PEDOT- or PANI-coated ITO substrates are    dried. For the drying, several processes are possible.    Conventionally, the films are dried in a drying oven between 110 and    200° C., preferably between 150 and 180° C., for from 1 to 10    minutes. However, newer drying processes, for example irradiation    with IR (infrared) light, also lead to very good results, the    irradiation time generally lasting only a few seconds. The low    molecular weight materials used are preferably thin layers between 5    and 30 nm of copper-phthalocyanine (CuPc). Conventionally, CuPc is    applied by vapor deposition in vacuum sublimation units. All HILs    have to not only inject holes very efficiently, but also adhere very    securely to ITO and glass; this is the case both for CuPc and for    PEDOT and PANI. A particularly low absorption in the visible region    and thus a high transparency is exhibited by PEDOT and PANI, which    is a further necessary property of the HIL.-   3. One or more hole transport layers (Hole Transport Layer ═HTL): in    most OLEDs, one or more HTLs are a prerequisite for good efficiency    and high stability. Very good results are achieved with a    combination of two layers, for example consisting of triarylamines    such as MTDATA    (4,4′,4″-tris(N-3-methylphenyl-N-phenylamino)triphenylamine) or    NaphDATA (4,4′,4″-tris(N-1-naphthyl-N-phenylamino)triphenylamine) as    the first HTL and NPB (N,N′-di(naphth-1-yl)-N,N′-diphenylbenzidine)    or spiro-TAD    (tetrakis(2,2′,7,7′-diphenylamino)spiro-9,9′-bifluorene) as the    second HTL. MTDATA or NaphDATA bring about an increase in the    efficiency in most OLEDs by approx. 20-40%; owing to the higher    glass transition temperature T_(g), preference is given to NaphData    (T_(g)=130° C.) over MTDATA (T_(g)=100° C.). As the second layer,    preference is given to spiro-TAD (T_(g)=130° C.) over NPB (T_(g)=95°    C.) owing to the higher T_(g). MTDATA and NaphDATA have a layer    thickness between 5 and 100 nm, preferably between 10 and 60 nm,    more preferably between 15 and 40 nm. For thicker layers, somewhat    higher voltages are required in order to achieve the same    brightness; at the same time, the number of defects is reduced.    spiro-TAD and NPB have a layer thickness between 5 and 150 nm,    preferably between 10 and 100 nm, more preferably between 20 and 60    nm. With increasing layer thickness of NPB and most other    triarylamines, higher voltages are required for equal brightnesses.    However, the layer thickness of spiro-TAD has only a slight    influence on the characteristic current-voltage electroluminescence    lines, i.e. the required voltage to achieve a particular brightness    depends only slightly upon the spiro-TAD layer thickness. Instead of    low molecular weight triarylamines, it is also possible to use high    molecular weight triarylamines. These are usually 0.1 to 30%    solutions which are applied in thin layers between 20 and 500 nm,    preferably between 40 and 150 nm of layer thickness, to the ITO    substrate or the HIL (e.g. PEDOT or PANI layer) by spincoating,    inkjet printing or other coating processes.-   4. Emission layer (Emission Layer=EML): this layer may partly    coincide with layers 3 and/or 5. It consists, for example, of a low    molecular weight matrix material and a low molecular weight guest    material, the phosphorescent dopant, for example CBP or one of the    above-described matrix materials A as the matrix material and    Ir(PPy)₃ as the dopant. Good results are achieved at a concentration    of 5-30% of Ir(PPy)₃ in CBP or in one of the above-described matrix    materials A at an EML layer thickness between 10 and 100 nm,    preferably between 10 and 50 nm. Instead of low molecular weight    light-emitting compounds, it is also possible to use high molecular    weight light-emitting compounds (polymers), in which case one or    else both components of the host-guest system may be high in    molecular weight.-   5. An electron transport and hole blocking layer (Hole Blocking    Layer=HBL): effective HBL materials have been found to be    particularly BCP (2,9-dimethyl-4,7-diphenyl-1,    10-phenanthroline=bathocuproin) or BAlq. Instead of low molecular    weight HBLs, it is also possible to use high molecular weight HBLs.    However, it has been found that OLEDs which comprise inventive    mixtures still exhibit very good results even without such a hole    blocking layer. Therefore, a hole blocking layer was not used in all    examples described below.-   6. Electron transport layer (Electron Transport Layer=ETL): metal    hydroxyquinolates are very suitable as ETL materials; particularly    aluminum tris-8-hydroxyquinolate (AlQ₃) has been found to be one of    the most stable electron conductors. Instead of low molecular weight    ETLs, it is also possible to use high molecular weight ETLs.    However, it has been found that OLEDs which comprise inventive    mixtures still exhibit very good results, in particular very low    voltages and high power efficiencies, even without such a hole    blocking layer. Therefore, an electron transport layer was not used    in all examples described below.-   7. Electron injection layer (Electron Injection Layer=EIL): a thin    layer having a layer thickness between 0.2 and 8 nm, preferably    between 0.5 and 5 nm, consisting of a material having a high    dielectric constant, in particular inorganic fluorides and oxides,    for example LiF, Li₂O, BaF₂, MgO, NaF and further materials, has    been found to be particularly good as the EIL. Especially in    combination with Al, this additional layer leads to a distinct    improvement in the electron injection and thus to improved results    with regard to lifetime, quantum efficiency and power efficiency.-   8. Cathode: here, generally metals, metal combinations or metal    alloys having a low work function are used, for example Ca, Ba, Cs,    K, Na, Mg, Al, In, Mg/Ag.-   9. a) Preparation of thin layers (2.-8.) of low molecular weight    compounds: all low molecular weight materials of the HIL, HTL, EML,    HBL, ETL, EIL and cathode are applied by vapor deposition in vacuum    sublimation units at a pressure of less than 10⁻⁵ mbar, preferably    less than 10 ⁻⁶ mbar, more preferably less than 10⁻⁷ mbar. The vapor    deposition rates may be between 0.01 and 10 nm/s, preferably 0.1 and    1 nm/s. More recent processes such as OPVD (organic physical vapor    deposition) or LITI (light induced thermal imaging) are likewise    suitable for the coating of low molecular weight materials, as are    further printing techniques. For doped layers, OPVD has great    potential because it is possible particularly efficiently to set any    desired mixing ratios. It is likewise possible to continuously    change the concentration of the dopants. Thus, the prerequisites for    improvement in the electroluminescent device are optimal for OPVD.    As described above, the preparation of the inventive devices can    also be carried out by specific printing processes (such as the LITI    mentioned). This has advantages both with regard to the scalability    of manufacture and with regard to the setting of mixing ratios in    blend layers used. For this purpose, it is, though, generally    necessary to prepare appropriate layers (for LITI: transfer layers)    which are only then transferred to the actual substrate.    -   b) Production of thin layers (2.-6.) of high molecular weight        compounds (polymers): these are usually 0.1 to 30% solutions or        dispersions which are applied in thin layers between 10 and 500        nm, preferably between 10 and 80 nm, of layer thickness to the        ITO substrate or layers below it by spincoating, inkjet        printing, LITI or other coating processes and printing        techniques.-   10. Encapsulation: effective encapsulation of the organic layers    including the EIL and the cathode is indispensable for organic    electroluminescent devices. When the organic display is formed on a    glass substrate, there are several options. One option is to    adhesive-bond the entire structure to a second glass or metal plate.    Two-component or UV-curing epoxy adhesives have been found to be    particularly suitable. The electroluminescent device may be    adhesive-bonded fully or else only at the edge. When the organic    display is adhesive-bonded only at the edge, the durability can be    additionally improved by adding what is known as a getter. This    getter consists of a very hygroscopic material, especially metal    oxides, for example BaO, CaO, etc., which binds ingressing water and    water vapors. An additional binding of oxygen is achieved with    getter materials, for example Ca, Ba, etc. In the case of flexible    substrates, particular attention should be paid to a high diffusion    barrier against water and oxygen. Here, especially laminates    composed of alternating thin plastics and inorganic layers (e.g.    SiO_(x) or SiN_(x)) have been found to be useful.    3. Device Examples

Here, the results of different OLEDs are compared. The basic structure,such as the materials used, degree of doping and their layerthicknesses, was identical for the example experiments for bettercomparability. Exclusively the host material in the emitter layer waschanged, and the examples were carried out with different tripletemitters. The first example describes a comparative standard accordingto the prior art, in which the emitter layer consists of the hostmaterial CBP and the guest material Ir(PPY)₃ (synthesized according toWO 02/060910). In addition, an OLED with an emitter layer consisting ofthe host material bis(9,9′-spirobifluoren-2-yl) ketone and the guestmaterial Ir(PPy)₃ is described. The second example describes a furthercomparison between CBP and bis(9,9′-spirobifluoren-2-yl) ketone (seeexample 1) with the red emitter Ir(BTP)₃ (synthesized according to WO02/060910). The third example describes two OLEDs, one a deep redemitter Ir(piq)₃ with bis(9,9′-spirobifluoren-2-yl) ketone and the othera red emitter Ir(FMepiq)₃ with bis(9,9′-spirobifluoren-2-yl) ketone.

Analogously to the abovementioned general process, green- andred-emitting OLEDs with the following structure were obtained: PEDOT 60nm (spincoated from water; PEDOT purchased from H.C. Starck; poly[3,4-ethylenedioxy-2,5-thiophene]) NaphDATA 20 nm (applied by vapordeposition; NaphDATA purchased from SynTec; 4,4′,4″-tris(N-1-naphthyl-N-phenylamino)- triphenylamine) S-TAD 20 nm (appliedby vapor deposition; S- TAD prepared according to WO 99/12888;2,2′,7,7′-tetrakis(diphenylamino)spirobifluorene) Emitter layer: CBP 20nm (applied by vapor deposition; CBP purchased from ALDRICH and purifiedfurther, finely sublimed twice more; 4,4′-bis(N-carbazolyl)biphenyl)(comparative standard) OR: bis(9,9′-spirobifluoren-2-yl) ketone 20 nm(applied by vapor deposition, synthesized and purified according toexample 1), in each case doped with 10% triplet emitter Ir(PPy)₃(applied by vapor deposition) OR: Ir(BTP)₃ (applied by vapor deposition)OR: Ir(piq)₃ (applied by vapor deposition) OR: Ir(FMepiq)₃ (applied byvapor deposition) Bathocuproin (BCP) 10 nm (applied by vapor deposition;BCP purchased from ABCR, used as obtained;2,9-dimethyl-4,7-diphenyl-1,10- phenanthroline); not used in allexamples AlQ₃ 10 nm (applied by vapor deposition; AlQ₃ purchased fromSynTec; tris(quinolinolato) aluminum(III)), not used in all examplesBa—Al 3 nm of Ba, 150 nm of Al thereon as the cathode

These OLEDs which were yet to be optimized were characterized in astandard manner; for this purpose, the electroluminescence spectra, theefficiency (measured in Cd/A) as a function of the brightness,calculated from current-voltage-brightness characteristic lines (IULcharacteristic lines), and the lifetime were determined.

For an overview, the triplet emitters used and the host materials usedare depicted below:

Use Example 1 Ir(PPy)₃

Electroluminescence Spectra:

The OLEDs, both the comparative standard OLED with CBP and OLED withbis(9,9′-spirobifluoren-2-yl) ketone as host material, exhibit greenemission, resulting from the Ir(PPy)₃ dopant.

Efficiency as a Function of Brightness:

For OLEDs produced with the CBP host material, a maximum efficiency ofabout 25 cd/A is typically obtained, and, for the reference illuminationdensity of 100 cd/m², 4.8 V are required. In contrast, OLEDs producedwith the bis(9,9′-spirobifluoren-2-yl) ketone host material exhibit amaximum efficiency of above 30 cd/A, while the required voltage for thereference illumination density of 100 cd/m² falls even to 4.6 V. Theefficiency is quite especially high when neither a pole blocking layer(HBL) nor an electron transport layer (ETL) is used, and the dopedemission layer (EML) extends as far as the cathode. A maximum efficiencyof above 35 cd/A is achieved, while the required voltage for thereference illumination density of 100 cd/m² falls even below 3 V.Particularly the power efficiency increases with use ofbis(9,9′-spirobifluoren-2-yl) ketone as the host material (π) comparedto CBP (♦) as the host material by from 20% to 100% (FIG. 1). Quiteespecially high power efficiencies up to 50 lm/W (□) are obtained whenneither a hole blocking layer (HBL) nor an electron transport layer(ETL) is used, and the doping of the emission layer (EML) extends as faras the cathode.

Lifetime Comparison:

The two lifetime curves (FIG. 2) with CBP and withbis(9,9′-spirobifluoren-2-yl) ketone as host materials (both used herewith hole blocking and electron transport layer) were shown in the samefigure for better comparability. The figure shows the profile of theillumination densities, measured in cd/m², with time. The lifetimerefers typically to the time after which only 50% of the initialillumination density is attained.

With CBP as the host material, a lifetime of approx. 150 hours isobtained at a starting brightness of 1400 cd/m², which corresponds to anaccelerated measurement, since the starting brightness is distinctlyabove the brightness which is required for typical activematrix-addressed display applications (250 cd/m²). Forbis(9,9′-spirobifluoren-2-yl) ketone, at the same starting brightness, alifetime of approx. 2000 hours is achieved, which corresponds to anincrease in the lifetime by about 1300%; this is also the case whenneither a hole blocking layer (HBL) nor an electron transport layer(ETL) is used.

From these measured lifetimes, lifetimes can then be calculated for astarting brightness of 250 cd/m². In the case of the CBP host material,only a lifetime of 4700 hours is obtained, which is distinctly below therequired 10 000 hours for a display application. In contrast, withbis(9,9′-spirobifluoren-2-yl) ketone, a lifetime of over 60 000 hours isachieved, which significantly exceeds the minimum requirements.

Use Example 2 Ir(BTP)₃

Analogous experiments were carried out with a red triplet emitterIr(BTP)₃.

Electroluminescence Spectra:

The OLEDs, both of the comparative standard OLED with CBP and the OLEDwith bis(9,9′-spirobifluoren-2-yl) ketone as the host material, exhibitred emission resulting from the Ir(BTP)₃ dopant. The two spectra areshown in FIG. 3.

Efficiency as a function of brightness:

For OLEDs produced with the CBP host material, typically a maximumefficiency of about 8 cd/A and, for the reference illumination densityof 100 cd/m², 6.2 V are required. In contrast, OLEDs produced with thehost material bis(9,9′-spirobifluoren-2-yl) ketone exhibit a maximumefficiency of above 11 cd/A, while the required voltage for thereference illumination density of 100 cd/m² falls even to 5.2 V (FIG.4).

Lifetime Comparison:

For better comparability, the two lifetime curves (FIG. 5) are shown inthe same figure. The figure shows the profile of the illuminationdensity, measured in cd/m², with time.

With CBP as the host material, a lifetime of approx. 53 hours isobtained at a starting brightness of nearly 1300 cd/m², which in thisexample too corresponds to an accelerated measurement. Withbis(9,9′-spirobifluoren-2-yl) ketone, a lifetime of approx. 275 hours isobtained at the same starting brightness, which corresponds to anincrease in the lifetime by about 500%.

From these measured lifetimes, it is possible to calculate lifetimes fora starting brightness of 250 cd/m². In the case of the CBP hostmaterial, only a lifetime of 1600 hours is obtained, which is distinctlybelow the required 10 000 hours for display applications. In contrast,with bis(9,9′-spirobifluoren-2-yl) ketone, a lifetime of above 8200hours is obtained, which closely approximates to the minimumrequirement.

Use Example 3 Ir(piq)₃ and Ir(FMepiq)₃

It was likewise possible to carry out experiments with a deep redtriplet emitter Ir(piq)₃ with bis(9,9′-spirobifluoren-2-yl) ketone and ared triplet emitter Ir(FMepiq)₃ with bis(9,9′-spirobifluoren-2-yl)ketone.

Electroluminescence Spectra:

The OLEDs exhibit a deep red emission and a red emission, resulting fromthe dopants Ir(piq)₃ (π) and Ir(FMepiq)₃ (♦). The two spectra are shownin FIG. 6. From the spectra, the CIE color coordinates calculated forIr(piq)₃ in bis(9,9′-spirobifluoren-2-yl) ketone (7t) are x=0.69;y=0.31, and those calculated for Ir(FMepiq)₃ inbis(9,9′-spirobifluoren-2-yl) ketone (♦) are x=0.66; y=0.34.

Efficiency as a Function of Brightness:

Both Ir(piq)₃ (π) in bis(9,9′-spirobifluoren-2-yl) ketone andIr(FMepiq)₃ (♦) in bis(9,9′-spirobifluoren-2-yl) ketone exhibit a veryhigh efficiency of max. 8 cd/A (for Ir(piq)₃ (π) at CIE colorcoordinates x=0.69, y=0.31) and 14 cd/A (for Ir(FMepiq)₃ (♦) at CIEcolor coordinates x=0.66, y=0.34) (FIG. 7). In both cases, the requiredvoltage for 100 cd/m² fell below 6 V.

Lifetime:

FIG. 8 shows the lifetime of Ir(piq)₃ with bis(9,9′-spirobifluoren-2-yl)ketone at constant current of 10 mA/cm² at a starting brightness ofapprox. 800 cd/r² and 5 mA/cm² at a starting brightness of approx. 400cd/m². In this case, a decline in the brightness of approx. 10% after1680 h at starting brightness 800 cd/m², and of approx. 5% after 1680 hat starting brightness 400 cd/m2. An extrapolation gives rise to alifetime of from approx. 5000 h at starting brightness 800 cd/m² and 20000 h at starting brightness 400 cd/m². For a starting brightness of 200cd/m², a lifetime of 80 000 h is calculated. Ir(FMepiq)₃ inbis(9,9′-spirobifluoren-2-yl) ketone exhibits a comparable lifetime.

Further device examples are compiled in table 2 which follows, theemission stemming in each case from the corresponding emitter. TABLE 2Max. Max. power efficiency efficiency Voltage (V) Lifetime (h)Experiment EML HBL ETL (cd/A) (Lm/W) at 100 cd/m² at 10 mA/cm²Comparative CBP: BCP AlQ₃ 25 12 4.8 150 example for 1) 20% Ir(ppy)₃ (10nm) (10 nm) (20 nm) Example 1a) M1: BCP AlQ₃ 30 25 4.6 400 20% Ir(ppy)₃(10 nm) (10 nm) (20 nm) Example 1b) M1: — — 35 50 3.0 370 20% Ir(ppy)₃(60 nm) Example 1c) M3: BCP AlQ₃ 28 20 4.5 250 20% Ir(ppy)₃ (10 nm) (10nm) (20 nm) Example 1d) M4: BCP AlQ₃ 39 22 4.9 220 20% Ir(ppy)₃ (10 nm)(10 nm) (20 nm) Example 1e) M4: — — 42 32 4.5 200 20% Ir(ppy)₃ (20 nm)Comparative CBP: BCP AlQ₃ 8 5 6.2 53 example for 2) 20% Ir(BTP)₃ (10 nm)(10 nm) (20 nm) Example 2a) M1: BCP AlQ₃ 11 8 5.2 275 20% Ir(BTP)₃ (10nm) (10 nm) (20 nm) Example 2b) M1: — — 11 10 4.1 250 20% Ir(BTP)₃ (20nm) Comparative CBP: BCP AlQ₃ 7 4 6.4 5000 example for 3) 20% Ir(piq)₃(10 nm) (10 nm) (extrapolated) (30 nm) Example 3a) M1: BCP AlQ₃ 8 6 5.820 000 20% Ir(piq)₃ (10 nm) (10 nm) (extrapolated) (30 nm) Example 3b)M1: — — 7 8 3.2 15 000 20% Ir(piq)₃ (extrapolated) (30 nm) Example 3c)M2: BCP AlQ₃ 7 5 6.1 20 000 20% Ir(piq)₃ (10 nm) (10 nm) (extrapolated)(30 nm) Example 4a) M1: BCP AlQ₃ 14 9 5.9 80 000 20% Ir(FMepiq)₃ (10 nm)(10 nm) (old: (30 nm) purported) Example 4b) M1: — — 15 12 4 80 000 20%Ir(FMepiq)₃ (30 nm) Example 4c) CBP: BCP AlQ₃ 10 6 7 10 000 comparison20% Ir(FMepiq)₃ (10 nm) (10 nm) (30 nm)

1. Mixtures comprising at least one matrix material A which contains astructural unit of the form C=Q in which Q has at least one non-bondingelectron pair and represents the element O, S, Se or N, and at least oneemission material B which is capable of emission and is a compoundwhich, upon suitable excitation, emits light, and contains at least oneelement of atomic number greater than
 20. 2. The mixture as claimed inclaim 1, characterized in that the matrix material A can form glasslikelayers.
 3. The mixture as claimed in claim 1, characterized in that thematrix material A has a glass transition temperature T_(g) (measured asthe pure substance) greater than 70° C.
 4. The mixture as claimed inclaim 1, characterized in that the matrix material A used is at leastone compound of the formula (1), formula (2) and/or formula (3)

where the symbols and indices are each defined as follows: X is the sameor different at each instance and is O, S or Se; Y at each instance isN; R¹, R² and R³ are the same or different at each instance and is H,CN, a straight-chain, branched or cyclic alkyl, alkoxy or alkylaminogroup having from 1 to 40 carbon atoms, in which one or more nonadjacentCH₂ groups is optionally replaced by —R⁴C═CR⁴—, —C≡C—, C═O, C═S, C=Se,C═NR⁴, —O—, —S—, —NR⁵— or —CONR⁶—, and in which one or more hydrogenatoms is optionally replaced by F, Cl, Br, I, or an aromatic orheteroaromatic system having from 1 to 40 carbon atoms, in which one ormore hydrogen atoms is optionally replaced by F, Cl, Br, I, and which isoptionally substituted by one or more nonaromatic R¹ radicals, and aplurality of substituents R¹ and/or R¹, R², either on the same ring oron the two different rings, optionally together in turn form a furthermono- or polycyclic, aliphatic or aromatic ring system; with the provisothat R¹=R²=R³ hydrogen; R⁴, R⁵ and R⁶ are the same or different at eachinstance and are H or an aliphatic or aromatic hydrocarbon radicalhaving from 1 to 20 carbon atoms.
 5. The mixture as claimed in claim 1,characterized in that the matrix material A used is at least onecompound of the formula (4) to (9)

where X is the same or different at each instance and is O, S or Se; Yat each instance is N; R¹, R² and R³ are the same or different at eachinstance and are H, CN, a straight-chain, branched or cyclic alkyl,alkoxy or alkylamino group having from 1 to 40 carbon atoms, in whichone or more nonadjacent CH₂ groups is optionally replaced by —R⁴C═CR⁴—,—C≡C—, C═O, C═S, C=Se, C═NR⁴, —O—, —S—, —NR⁵— or —CONR⁶—, and in whichone or more hydrogen atoms is optionally replaced by F, Cl, Br, I, or anaromatic or heteroaromatic system having from 1 to 40 carbon atoms, inwhich one or more hydrogen atoms is optionally replaced by F, Cl, Br, I,and which is optionally substituted by one or more nonaromatic R¹radicals, and a plurality of substituents R¹ and/or R¹, R², either onthe same ring or on the two different rings, optionally together in turnform a further mono- or polycyclic, aliphatic or aromatic ring system;with the proviso that R¹=R²=R³≠hydrogen; R⁴, R⁵ and R⁶ are the same ordifferent at each instance and are H or an aliphatic or aromatichydrocarbon radical having from 1 to 20 carbon atoms and Z is the sameor different at each instance and is CR¹ or N.
 6. The mixture as claimedin claim 5, characterized in that the matrix material A used is at leastone compound of the formula (1) to (9) in which the symbols used are:

X is the same or different at each instance and is O or S, Y at eachinstance is N; Z at each instance is CR¹; R¹, R² and R³ are the same ordifferent at each instance and are H, a straight-chain, branched orcyclic alkyl group which has from 1 to 40 carbon atoms and no hydrogenatoms in the α-position to the keto or imine function, in which one ormore nonadjacent CH₂ groups is optionally replaced by —R⁴C═CR⁴—, —C≡C—,C═O, C═S, C=Se, C═NR⁴, —O—, —S—, —NR⁵— or —CONR⁶—, and in which one ormore hydrogen atoms is optionally replaced by F, Cl, Br, I, or anaromatic or heteroaromatic system having from 1 to 40 carbon atoms, inwhich one or more hydrogen atoms may be replaced by F, Cl, Br, I, andwhich is optionally substituted by one or more nonaromatic R¹ radicals,and a plurality of substituents R¹ and/or R¹, R², either on the samering or on the different rings, optionally together in turn form afurther mono- or polycyclic, aliphatic or aromatic ring system, R⁴, R⁵and R⁶ are the same or different at each instance and are H or analiphatic or aromatic hydrocarbon radical having from 1 to 20 carbonatoms.
 7. The mixture as claimed in claim 1, characterized in that thematrix material A used is at least one compound of the formula (10) to(15)

where Y at each instance is N; Z is the same or different at eachinstance and is CR¹ or N; R¹, R² and R³ are the same or different ateach instance and are H, CN, a straight-chain, branched or cyclic alkyl,alkoxy or alkylamino group having from 1 to 40 carbon atoms, in whichone or more nonadjacent CH₂ groups is optionally replaced by —R⁴C═CR⁴—,—C≡C—, C═O, C═S, C=Se, C═NR⁴, —O—, —S—, —NR⁵— or —CONR⁶—, and in whichone or more hydrogen atoms is optionally replaced by F, Cl, Br, I, or anaromatic or heteroaromatic system having from 1 to 40 carbon atoms, inwhich one or more hydrogen atoms is optionally replaced by F, Cl, Br, I,and which is optionally substituted by one or more nonaromatic R¹radicals, and a plurality of substituents R¹ and/or R¹, R², either onthe same ring or on the two different rings, optionally together in turnform a further mono- or polycyclic, aliphatic or aromatic ring system,with the proviso that R¹=R²=R³≠hydrogen; R⁴, R⁵ and R⁶ are the same ordifferent at each instance and are H or an aliphatic or aromatichydrocarbon radical having from 1 to 20 carbon atoms, Ar is the same ordifferent at each instance and is an aromatic or heteroaromatic systemhaving from 2 to 40 carbon atoms, in which one or more hydrogen atoms isoptionally replaced by F, Cl, Br, I, and which is optionally substitutedby one or more nonaromatic R¹ radicals, and a plurality of substituentsR¹, either on the same ring or on different rings, optionally togetherin turn form a further mono- or polycyclic, aliphatic or aromatic ringsystem; n is the same or different at each instance and is 0 or
 1. 8.The mixture as claimed in claim 1, characterized in that the emitter Bused is at least one compound which, upon suitable excitation, emitslight and contains at least one atom of atomic number greater than 38and less than
 84. 9. The mixture as claimed in claim 8, characterized inthat the emitter B used is at least one compound which, upon suitableexcitation, emits light and contains at least one atom of atomic numbergreater than 56 and less than
 80. 10. The mixture as claimed in claim 9,characterized in that the emitter B used is at least one compound which,upon suitable excitation, emits light and contains at least one atomfrom the group of molybdenum, tungsten, rhenium, ruthenium, osmium,rhodium, iridium, palladium, platinum, silver, gold or europium.
 11. Themixture as claimed in claim 1, characterized in that the emitter B usedis at least one compound of the formula (16) to (19)

where the symbols used are: DCy is the same or different at eachinstance and is a cyclic group which contains at least one donor atomvia which the cyclic group is bonded to the metal atom, and whichoptionally bear one or more substituents R⁹; the DCy and CCy groups arejoined together via a covalent bond; CCy is the same or different ateach instance and is a cyclic group which contains a carbon atom viawhich the cyclic group is bonded to the metal and which optionally bearone or more substituents R⁹; R⁹ is the same or different at eachinstance and is H, F, Cl, Br, I, NO₂, CN, a straight-chain or branchedor cyclic alkyl or alkoxy group having from 1 to 40 carbon atoms, inwhich one or more nonadjacent CH₂ groups is optionally replaced by—CR⁴═CR⁴—, —C≡C—, C═O, C═S, C=Se, C═NR⁴, —O—, —S—, —NR⁵— or —CONR⁶—, andin which one or more hydrogen atoms is optionally replaced by F, or anaromatic or heteroaromatic system which has from 4 to 40 carbon atomsand is optionally substituted by one or more nonaromatic R⁹ radicals;and a plurality of substituents R⁹, either on the same ring or on thetwo different rings, optionally together in turn form a further mono- orpolycyclic, aliphatic or aromatic ring system; L is the same ordifferent at each instance and is a bidentate chelating ligand; R⁴, R⁵and R⁶ are the same or different at each instance and is H or analiphatic or aromatic hydrocarbon radical having from 1 to 20 carbonatoms.
 12. The mixture as claimed in claim 1, characterized in that thematrix material contains one or more polymers or dentrimers.
 13. Themixture as claimed in claim 12, characterized in that the polymer isconjugated, semiconjugated or nonconjugated.
 14. The mixture as claimedin claim 12, characterized in that the polymer is selected from thegroup of the polyfluorenes, poly-spiro-bifluorenes,poly-para-phenylenes, polycarbazoles, polyvinylcarbazoles,polythiophenes, or else from copolymers which have a plurality of theseunits.
 15. The mixture as claimed in claim 1, characterized in that themixture contains between 1 to 99% by weight of emitter B based on theoverall mixture of emitter B and matrix material A.
 16. Compounds of theformula (10a) to (15)

in which the symbols Y at each instance is N; Z is the same or differentat each instance and is CR¹ or N; R¹, R² and R³ are the same ordifferent at each instance and are H, CN, a straight-chain, branched orcyclic alkyl, alkoxy or alkylamino group having from 1 to 40 carbonatoms in which one or more nonadjacent CH₂ groups is optionally replacedby —R⁴C═CR⁴—, —C≡C—, C═O, C═S, C=Se, C═NR⁴, —O—, —S—, —NR⁵— or —CONR⁶—,and in which one or more hydrogen atoms is optionally replaced by F, Cl,Br, I, or an aromatic or heteroaromatic system having from 1 to 40carbon atoms, in which one or more hydrogen atoms is optionally replacedby F, Cl, Br, I, and which is optionally substituted by one or morenonaromatic R¹ radicals, and a plurality of substituents R¹ and/or R¹,R², either on the same ring or on the two different rings optionallytogether in turn form a further mono- or polycyclic, aliphatic oraromatic ring system; with the proviso that R¹=R²=R³≠hydrogen; R⁴, R⁵and R⁶ are the same or different at each instance and are H or analiphatic or aromatic hydrocarbon radical having from 1 to 20 carbonatoms, Ar is the same or different at each instance and is an aromaticor heteroaromatic system having from 2 to 40 carbon atoms, in which oneor more hydrogen atoms is optionally replaced by F, Cl, Br, I, and whichis optionally substituted by one or more nonaromatic R¹ radicals, and aplurality of substituents R¹, either on the same ring or on differentrings, optionally together in turn form a further mono- or polycyclic,aliphatic or aromatic ring system; E is the same or different at eachinstance and is C or N; R⁷ is the same or different at each instance andis an alkyl, alkoxy or alkylamino group having from 1 to 40 carbonatoms, in which one or more CH₂ groups is optionally replaced by—R⁴C═CR⁴—, —C≡C—, C═O, C═S, C=Se, C═NR⁴, —O—, —S—, —NR⁴ or —CONR⁴—, andin which one or more hydrogen atoms is optionally replaced by F, Cl, Br,I, with the proviso that no hydrogen atoms are bonded in the α-positionto the carbonyl group, or an aromatic group which may optionally besubstituted by halogen, alkyl, trifluoromethyl, hydroxyl, —SH, —S-alkyl,alkoxy, nitro, cyano, —COOH, —COOalkyl, —NH₂, -Nalkyl, benzyl orbenzoyl, or a larger aromatic system having from 2 to 40 carbon atoms,in which one or more hydrogen atoms is optionally replaced by F, Cl, Br,I, and which is optionally substituted by one or more nonaromatic R¹radicals, and a plurality of substituents R¹ may in turn form a furthermono- or polycyclic, aliphatic or aromatic ring system; A¹ at eachinstance is R⁸ or CO—R⁷ when X═C or is a free electron pair when X═N; A²at each instance is R⁸ or CO—R⁷ when X═C or is a free electron pair whenX═N; A³ at each instance is R⁸ or CO—R⁷ when X═C or is a free electronpair when X═N; R⁸ is the same or different at each instance and is H, F,Cl, Br, I, CN, NO₂, a straight-chain or branched or cyclic alkyl grouphaving from 1 to 40 carbon atoms, in which one or more nonadjacent CH₂groups is optionally replaced by —R⁴C═CR⁴—, —C≡C—, C═S, C═Se, C═NR⁴,—O—, —S—, —NR⁴— or —CONR⁴—, and in which one or more hydrogen atoms isoptionally replaced by F, Cl, Br, I, or an aromatic or heteroaromaticsystem having from 1 to 40 carbon atoms, in which one or more hydrogenatoms is optionally replaced by F, Cl, Br, I, and which is optionallysubstituted by one or more nonaromatic R¹ radicals, and a plurality ofsubstituents R¹ and/or R¹/R⁴, either on the same ring or on thedifferent rings, optionally together in turn form a further mono- orpolycyclic, aliphatic or aromatic ring system; with the proviso that,for the compound of the formula (10a), only the following combinationsare permitted for the symbols described, where R⁸ and R⁴ can be selectedfreely according to the definition: when R⁷ is an alkyl group withoutα-hydrogen atoms, the symbols Z, E, A¹, A² and A³ can be selected freelyaccording to the definition; when R⁷ is an aromatic group and at leastone Z is N, the symbols E, A¹, A² and A³ can be selected freelyaccording to the definition; when R⁷ is an aromatic group and at leastone Z is a CR¹ group where R¹ is other than H, the symbols E, A¹, A² andA³ can be selected freely according to the definition; when R⁷ is anaromatic group and all Z are CH and at least one symbol E is N, thesymbols A¹, A² and A³ can be selected freely according to thedefinition; when R⁷ is an aromatic group, all Z are CH and all E are C,at least one of the symbols A¹, A² and/or A³ has to be an R⁸ group otherthan alkyl, while the two other groups can be selected freely accordingto the definition; when R⁷ is an aromatic group, all Z are CH, all E areC and the two symbols A¹ and A² are selected freely according to thedefinition, at least one of the two symbols being a group other than H,the symbol A³ is a CO—R⁷ group where R⁷ here can be selected freelyaccording to the definition; when R⁷ is a larger aromatic system, forexample fluorene, spirobifluorene, triarylamine, etc., the symbols Z, E,A¹, A² and A³ can be selected freely according to the definition.
 17. Anelectronic component comprising at least one mixture as claimed inclaim
 1. 18. The electronic component as claimed in claim 17,characterized in that it is an organic light-emitting diode (OLED), anorganic integrated circuit (O-IC), an organic field-effect transistor(OFET), an organic thin-film transistor (OTFT), an organic solar cell(O-SC) or an organic laser diode (O-laser).
 19. The electronic componentas claimed in claim 17, characterized in that the electronic componentis an organic light-emitting diode (OLED) which comprises at least onehole injection layer and/or at least one hole transport layer and/or atleast one hole blocking layer and/or at least one electron transportlayer and/or at least one electron injection layer and/or furtherlayers, and which comprises at least one mixture comprising at least onematrix material A which contains a structural unit of the form C—Q inwhich Q has at least one non-bonding electron pair and represents theelement O, S, Se or N, and at least one emission material B which iscapable of emission and is a compound which, upon suitable excitation,emits light, and contains at least one element of atomic number greaterthan 20 in the emission layer.
 20. The electronic component as claimedin claim 19, characterized in that a mixture comprising at least onematrix material A which contains a structural unit of the form C═Q inwhich Q has at least one non-bonding electron pair and represents theelement O, S, Se or N, and at least one emission material B which iscapable of emission and is a compound which, upon suitable excitation,emits light, and contains at least one element of atomic number greaterthan 20 without the use of a separate hole blocking layer directlyadjoins an electron transport layer.
 21. The electronic component asclaimed in claim 19, characterized in that the mixture comprising atleast one matrix material A which contains a structural unit of the formC═Q in which Q has at least one non-bonding electron pair and representsthe element Q, S, Se or N, and at least one emission material B which iscapable of emission and is a compound which, upon suitable excitation,emits light, and contains at least one element of atomic number greaterthan 20 without use of a separate hole blocking layer and of a separateelectron transport layer directly adjoins an electron injection layer orthe cathode.